TWI686461B - A silicon etchant with high si/sio etching selectivity and its application - Google Patents
A silicon etchant with high si/sio etching selectivity and its application Download PDFInfo
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- TWI686461B TWI686461B TW108104163A TW108104163A TWI686461B TW I686461 B TWI686461 B TW I686461B TW 108104163 A TW108104163 A TW 108104163A TW 108104163 A TW108104163 A TW 108104163A TW I686461 B TWI686461 B TW I686461B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000010703 silicon Substances 0.000 title claims abstract description 100
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 85
- 238000005530 etching Methods 0.000 title claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 19
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 28
- 239000004065 semiconductor Substances 0.000 claims description 13
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- RNVYQYLELCKWAN-UHFFFAOYSA-N solketal Chemical compound CC1(C)OCC(CO)O1 RNVYQYLELCKWAN-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 229940050176 methyl chloride Drugs 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 claims description 2
- GVIVQCNNFDHBAG-UHFFFAOYSA-N 2,2-dimethyl-1,3-dioxole Chemical compound CC1(C)OC=CO1 GVIVQCNNFDHBAG-UHFFFAOYSA-N 0.000 claims 1
- YYEZYENJAMOWHW-UHFFFAOYSA-N 2-(2,2-dimethyl-1,3-dioxolan-4-yl)ethanol Chemical compound CC1(C)OCC(CCO)O1 YYEZYENJAMOWHW-UHFFFAOYSA-N 0.000 claims 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 abstract description 14
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 14
- 229910052682 stishovite Inorganic materials 0.000 abstract description 14
- 229910052905 tridymite Inorganic materials 0.000 abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 description 41
- 229910052814 silicon oxide Inorganic materials 0.000 description 15
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 235000012431 wafers Nutrition 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZVVOWUWUXVCFHC-UHFFFAOYSA-N CC1(OCC(O1)CCO)C.CC1(OCC(O1)CCO)C Chemical compound CC1(OCC(O1)CCO)C.CC1(OCC(O1)CCO)C ZVVOWUWUXVCFHC-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 2
- ZYHICNHOBCFQCD-UHFFFAOYSA-N CC1(OCC(O1)CN)C.CC1(OCC(O1)CN)C Chemical compound CC1(OCC(O1)CN)C.CC1(OCC(O1)CN)C ZYHICNHOBCFQCD-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- CQBPOPVKDNHISM-UHFFFAOYSA-N propane-1,2,3-triol;propan-2-one Chemical compound CC(C)=O.OCC(O)CO CQBPOPVKDNHISM-UHFFFAOYSA-N 0.000 description 2
- HXOYWCSTHVTLOW-UHFFFAOYSA-N (2,2-dimethyl-1,3-dioxolan-4-yl)methanamine Chemical compound CC1(C)OCC(CN)O1 HXOYWCSTHVTLOW-UHFFFAOYSA-N 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- SIJBDWPVNAYVGY-UHFFFAOYSA-N 2,2-dimethyl-1,3-dioxolane Chemical compound CC1(C)OCCO1 SIJBDWPVNAYVGY-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BNPOTXLWPZOESZ-UHFFFAOYSA-N CC1(C)OC(CCl)CO1 Chemical compound CC1(C)OC(CCl)CO1 BNPOTXLWPZOESZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RVPAGRVOSVAXSH-UHFFFAOYSA-N n,n-dimethylmethanamine;ethanol Chemical compound CCO.CN(C)C RVPAGRVOSVAXSH-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
- H01L21/30608—Anisotropic liquid etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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Abstract
Description
本發明係關於一種具有高矽/二氧化矽蝕刻的選擇比的矽蝕刻劑及其應用。特別的，上述具有高矽/二氧化矽蝕刻的選擇比的矽蝕刻劑包含至少一縮酮類化合物和至少一四級銨氫氧化物，且矽/二氧化矽蝕刻選擇比大於500。該具有高矽/二氧化矽蝕刻的選擇比的矽蝕刻劑是應用在半導體奈米製程的矽圖案蝕刻程序。 The invention relates to a silicon etchant with high silicon/silicon dioxide etching selectivity and its application. In particular, the above-mentioned silicon etchant with a high silicon/silica etching selectivity includes at least a ketal compound and at least a quaternary ammonium hydroxide, and the silicon/silica etching selectivity is greater than 500. The silicon etchant with a high silicon/silicon dioxide etching selectivity is used in the silicon pattern etching process of semiconductor nano-processes.
在半導體先進的奈米製程，必須進行微小線寬的矽圖案蝕刻程序，且同時需要保護二氧化矽絕緣層及介電層結構，因此在半導體先進的奈米製程中需要使用特殊的矽蝕刻劑。 In the advanced nano process of semiconductor, a silicon pattern etching process with a small line width must be performed, and at the same time, the structure of the silicon dioxide insulating layer and the dielectric layer needs to be protected. Therefore, a special silicon etchant is required in the advanced semiconductor nano process .
習知的矽蝕刻劑的組成包含四級銨、有機胺和多元醇，但是此類型的矽蝕刻劑會腐蝕二氧化矽，因此無法保護 二氧化矽絕緣層和介電層結構，所以不能應用在半導體奈米製程中的矽圖案蝕刻程序。 The composition of the conventional silicon etchant contains quaternary ammonium, organic amines and polyols, but this type of silicon etchant corrodes silicon dioxide and cannot be protected Silicon dioxide insulating layer and dielectric layer structure, so it can not be used in the silicon pattern etching process in semiconductor nano process.
目前半導體奈米製程的蝕刻程序所使用的矽蝕刻劑未能有效保護二氧化矽絕緣層和介電層結構，所以無法在更先進的製程達到微縮線寬的矽圖案蝕刻的效果，導致製程良率過低，無法符合產業需求。有鑒於此，開發一具有高蝕刻選擇性的矽蝕刻劑是目前半導體產業亟需研究開發的技術領域。 At present, the silicon etchant used in the etching process of the semiconductor nano process fails to effectively protect the structure of the silicon dioxide insulating layer and the dielectric layer, so it is impossible to achieve the effect of etching the silicon pattern with a reduced line width in a more advanced process, resulting in a good process The rate is too low to meet industry needs. In view of this, the development of a silicon etchant with high etch selectivity is a technical field in which the semiconductor industry urgently needs research and development.
鑒於上述之發明背景，為了符合產業上之要求，本發明之第一目的在於提供一種矽蝕刻劑，該矽蝕刻劑具有高矽/二氧化矽(Si/SiO2)蝕刻的選擇比，因此能有效地保護二氧化矽絕緣層和介電層結構，並應用在半導體奈米製程的矽圖案蝕刻程序。 In view of the above background of the invention, in order to meet the requirements of the industry, the first object of the present invention is to provide a silicon etchant which has a high silicon/silicon dioxide (Si/SiO2) etching selectivity and is therefore effective It protects the structure of the silicon dioxide insulating layer and the dielectric layer, and is used in the silicon pattern etching process of the semiconductor nano process.
具體地，本發明所提供的矽蝕刻劑具有大於500：1矽/二氧化矽蝕刻的選擇比；所述的矽蝕刻劑包含至少一縮酮類化合物和至少一四級銨氫氧化物；以該矽蝕刻劑的總重量計，該縮酮類化合物所佔的重量百分比是20~99重量%，該四級銨氫氧化物所佔的重量百分比是0.1~10重量%。較佳地，該縮酮類化合物所佔的重量百分比是60~90重量%。 Specifically, the silicon etchant provided by the present invention has a selectivity ratio of greater than 500:1 silicon/silica etching; the silicon etchant includes at least one ketal compound and at least one quaternary ammonium hydroxide; Based on the total weight of the silicon etchant, the weight percentage of the ketal compound is 20 to 99% by weight, and the weight percentage of the quaternary ammonium hydroxide is 0.1 to 10% by weight. Preferably, the weight percentage of the ketal compound is 60-90% by weight.
本發明所述的縮酮類化合物之一具有以下的結構通式：其中R1、R2、R3及R4可獨立為相同或不同之直鏈或分支的碳數1~6的烷基。 One of the ketal compounds described in the present invention has the following general formula: wherein R 1 , R 2 , R 3 and R 4 can independently be the same or different straight-chain or branched C 1-6 alkyl groups .
較佳地，本發明所述的縮酮類化合物還包含2,2-二甲基-1,3-二氧戊環-4-甲醇(丙酮縮甘油，2,2-Dimethyl-1,3-dioxolane-4-methanol)、2,2-二甲基-1,3-二氧戊環-4-乙醇(2,2-dimethyl-1,3-dioxolane-4-ethanol)、2,2-二甲基-1,3-二氧戊環-4-甲基氯(4-Chloromethyl-2,2-dimethyl-1,3-dioxolane)和2,2-二甲基-1,3-二氧戊環-4-甲胺(2,2-dimethyl-1,3-dioxolane-4-methylamine)。 Preferably, the ketal compound of the present invention further comprises 2,2-dimethyl-1,3-dioxolane-4-methanol (acetone glycidol, 2,2-Dimethyl-1,3- dioxolane-4-methanol), 2,2-dimethyl-1,3-dioxolane-4-ethanol (2,2-dimethyl-1,3-dioxolane-4-ethanol), 2,2-bis Methyl-1,3-dioxolane-4-methyl chloride (4-Chloromethyl-2,2-dimethyl-1,3-dioxolane) and 2,2-dimethyl-1,3-dioxolane Cyclo-4-methylamine (2,2-dimethyl-1,3-dioxolane-4-methylamine).
本發明所述的四級銨氫氧化物具有R5R6R7R8N+OH-的結構通式，其中R5、R6、R7及R8可獨立為相同或不同之直鏈或分支的碳數1-4的烷基或碳數1-4的醇。 The quaternary ammonium hydroxide according to the present invention has the general structural formula of R 5 R 6 R 7 R 8 N + OH - , wherein R 5 , R 6 , R 7 and R 8 may independently be the same or different straight chains Or a branched C 1-4 alkyl group or a C 1-4 alcohol.
本發明之第二目的在於提供一種矽圖案的蝕刻方法，該矽圖案的蝕刻方法係使用本發明第一目的所述的矽蝕刻劑。該矽蝕刻劑具有高矽/二氧化矽(Si/SiO2)蝕刻的選擇比，因此能有效地保護二氧化矽絕緣層和介電層結構，減少蝕刻程序中二氧化矽絕緣層及介電層結構的腐蝕損害，非常適合 應用在半導體先進的奈米製程進行微小線寬的矽圖案蝕刻。 The second object of the present invention is to provide a method for etching a silicon pattern, which uses the silicon etchant described in the first object of the present invention. The silicon etchant has a high silicon/silicon dioxide (Si/SiO2) etching selectivity, so it can effectively protect the structure of the silicon dioxide insulating layer and the dielectric layer, reducing the silicon dioxide insulating layer and the dielectric layer in the etching process Corrosion damage to the structure, very suitable It is used in the advanced nano process of semiconductor to etch silicon pattern with tiny line width.
具體的，上述的矽蝕刻劑對矽/二氧化矽(Si/SiO2)蝕刻的選擇比是大於500：1。較佳地，上述的矽蝕刻劑對矽/二氧化矽(Si/SiO2)蝕刻的選擇比是在1000：1以上。 Specifically, the selection ratio of the above silicon etchant to silicon/silicon dioxide (Si/SiO2) etching is greater than 500:1. Preferably, the selection ratio of the above silicon etchant to silicon/silicon dioxide (Si/SiO2) etching is above 1000:1.
有關本發明之前述及其他技術內容、特點與功效，在以下配合參考圖式之一較佳實施例的詳細說明中]，將可清楚的呈現。為了能徹底地瞭解本發明，將在下列的描述中提出詳盡的步驟及其組成。顯然地，本發明的施行並未限定於該領域之技藝者所熟習的特殊細節。另一方面，眾所周知的組成或步驟並未描述於細節中，以避免造成本發明不必要之限制。本發明的較佳實施例會詳細描述如下，然而除了這些詳細描述之外，本發明還可以廣泛地施行在其他的實施例中，且本發明的範圍不受限定，其以之後的專利範圍為準。 The foregoing and other technical contents, features and effects of the present invention will be clearly presented in the following detailed description with reference to one of the preferred embodiments of the drawings]. In order to thoroughly understand the present invention, detailed steps and their composition will be presented in the following description. Obviously, the implementation of the present invention is not limited to the specific details familiar to those skilled in the art. On the other hand, well-known components or steps are not described in detail to avoid unnecessary limitation of the present invention. The preferred embodiments of the present invention will be described in detail below. However, in addition to these detailed descriptions, the present invention can be widely implemented in other embodiments, and the scope of the present invention is not limited, which is subject to the scope of the subsequent patent .
根據本發明第一實施例，本發明提供一種矽蝕刻劑，該矽蝕刻劑包含至少一縮酮類化合物和至少一四級銨氫氧化物，以該矽蝕刻劑的總重量計，該縮酮類化合物所佔的重量百分比是20~99重量%，該四級銨氫氧化物所佔的重量百 分比是0.1~10重量%。 According to a first embodiment of the present invention, the present invention provides a silicon etchant comprising at least one ketal compound and at least one quaternary ammonium hydroxide. Based on the total weight of the silicon etchant, the ketal The weight percentage of the compounds is 20~99% by weight, and the weight of the quaternary ammonium hydroxide is 100 The fractional ratio is 0.1 to 10% by weight.
於一較佳實施例，本發明所述的矽蝕刻劑，以該矽蝕刻劑的總重量計，該縮酮類化合物所佔的重量百分比是60~90重量%。 In a preferred embodiment, in the silicon etchant of the present invention, based on the total weight of the silicon etchant, the weight percentage of the ketal compound is 60 to 90% by weight.
於一實施例，本發明所述的縮酮類化合物之一具有以下的結構通式：其中R1、R2、R3及R4可獨立為相同或不同之直鏈或分支的碳數1~6的烷基。 In one embodiment, one of the ketal compounds of the present invention has the following structural formula: wherein R 1 , R 2 , R 3 and R 4 can independently be the same or different linear or branched carbon number 1 ~6 alkyl.
於一較佳實施例，本發明所述的縮酮類化合物包含：2,2-二甲基-1,3-二氧戊環-4-甲醇(丙酮縮甘油，2,2-Dimethyl-1,3-dioxolane-4-methanol)、2,2-二甲基-1,3-二氧戊環-4-乙醇(2,2-dimethyl-1,3-dioxolane-4-ethanol)、2,2-二甲基-1,3-二氧戊環-4-甲基氯(4-Chloromethyl-2,2-dimethyl-1,3-dioxolane)和2,2-二甲基-1,3-二氧戊環-4-甲胺(2,2-dimethyl-1,3-dioxolane-4-methylamine)。 In a preferred embodiment, the ketal compounds of the present invention include: 2,2-dimethyl-1,3-dioxolane-4-methanol (acetone glycidol, 2,2-Dimethyl-1 ,3-dioxolane-4-methanol), 2,2-dimethyl-1,3-dioxolane-4-ethanol (2,2-dimethyl-1,3-dioxolane-4-ethanol), 2, 2-Dimethyl-1,3-dioxolane-4-methyl chloride (4-Chloromethyl-2,2-dimethyl-1,3-dioxolane) and 2,2-dimethyl-1,3- Dioxolane-4-methylamine (2,2-dimethyl-1,3-dioxolane-4-methylamine).
上述之2,2-二甲基-1,3-二氧戊環-4-甲醇(丙酮縮甘油，2,2-Dimethyl-1,3-dioxolane-4-methanol)具有如下的結構式。 The above 2,2-dimethyl-1,3-dioxolane-4-methanol (acetone glycidol, 2,2-Dimethyl-1,3-dioxolane-4-methanol) has the following structural formula.
上述之2,2-二甲基-1,3-二氧戊環-4-乙醇(2,2-dimethyl-1,3-dioxolane-4-ethanol)具有如下的結構式。 The aforementioned 2,2-dimethyl-1,3-dioxolane-4-ethanol (2,2-dimethyl-1,3-dioxolane-4-ethanol) has the following structural formula.
上述之2,2-二甲基-1,3-二氧戊環-4-甲基氯(4-Chloromethyl-2,2-dimethyl-1,3-dioxolane)具有如下的結構式。 The above 2,2-dimethyl-1,3-dioxolane-4-methyl chloride (4-Chloromethyl-2,2-dimethyl-1,3-dioxolane) has the following structural formula.
上述之2,2-二甲基-1,3-二氧戊環-4-甲胺(2,2-dimethyl-1,3-dioxolane-4-methylamine)具有如下的結構式。 The above 2,2-dimethyl-1,3-dioxolane-4-methylamine (2,2-dimethyl-1,3-dioxolane-4-methylamine) has the following structural formula.
於一實施例，本發明所述的四級銨氫氧化物具有R5R6R7R8N+OH-的結構通式，其中R5、R6、R7及R8可獨立為 相同或不同之直鏈或分支的碳數1-4的烷基或碳數1-4的醇。 In one embodiment, the quaternary ammonium hydroxide according to the present invention has the structural formula of R 5 R 6 R 7 R 8 N + OH - , wherein R 5 , R 6 , R 7 and R 8 may be independently the same Or different linear or branched C 1-4 alkyl groups or C 1-4 alcohols.
於一較佳實施例，本發明所述的四級銨氫氧化物包含：氫氧化四甲基銨(TMAH；Tetramethylammonium hydroxide)、氫氧化四乙基銨(TEAH；Tetraethylammonium hydroxide)、氫氧化乙基三甲基銨(ETMAH；Ethyltrimethylammonium Hydroxide)和氫氧化2-羥基乙基三甲基銨(2-Hydroxyethyl trimethylammonium hydroxide)。 In a preferred embodiment, the quaternary ammonium hydroxide of the present invention includes: tetramethylammonium hydroxide (TMAH; Tetramethylammonium hydroxide), tetraethylammonium hydroxide (TEAH; Tetraethylammonium hydroxide), ethyl hydroxide Trimethylammonium (ETMAH; Ethyltrimethylammonium Hydroxide) and 2-Hydroxyethyl trimethylammonium hydroxide (2-Hydroxyethyl trimethylammonium hydroxide).
於一實施例，本發明所述的矽蝕刻劑還包含一水性介質。較佳地，該水性介質是水。 In one embodiment, the silicon etchant of the present invention further includes an aqueous medium. Preferably, the aqueous medium is water.
於一代表實施例，本發明所述的矽蝕刻劑的組成是上述之縮酮類化合物、上述之四級銨氫氧化物和水。其中以該矽蝕刻劑的總重量計，該縮酮類化合物所佔的重量百分比是20~99重量%，該四級銨氫氧化物所佔的重量百分比是0.1~10重量%，不足重量百分之百的部分，只需要補充水分直到總重量為百分之百。 In a representative embodiment, the composition of the silicon etchant according to the present invention is the aforementioned ketal compound, the aforementioned quaternary ammonium hydroxide and water. Based on the total weight of the silicon etchant, the weight percentage of the ketal compound is 20~99% by weight, and the weight percentage of the quaternary ammonium hydroxide is 0.1~10% by weight, less than 100% by weight Only need to add water until the total weight is 100%.
於一實施例，本發明所述的矽蝕刻劑是一具有矽/二氧化矽(Si/SiO2)蝕刻的選擇比大於500：1的矽蝕刻劑。 In one embodiment, the silicon etchant of the present invention is a silicon etchant with a silicon/silicon dioxide (Si/SiO 2 ) etching selectivity greater than 500:1.
於一較佳實施例，本發明所述的矽蝕刻劑是一具有矽/二氧化矽(Si/SiO2)蝕刻的選擇比大於1000：1的矽蝕刻劑 In a preferred embodiment, the silicon etchant of the present invention is a silicon etchant with a silicon/silicon dioxide (Si/SiO 2 ) etching selectivity greater than 1000:1
於一實施例，本發明所述的矽蝕刻劑是應用在半導體奈米製程的矽圖案蝕刻程序。 In one embodiment, the silicon etchant described in the present invention is applied to a silicon pattern etching process in a semiconductor nano process.
根據本發明第二實施例，本發明提供一種矽圖案的蝕刻方法，該矽圖案的蝕刻方法係使用本發明第一實施例所述的矽蝕刻劑。該矽蝕刻劑具有高矽/二氧化矽(Si/SiO2)蝕刻的選擇比，因此能有效地保護二氧化矽絕緣層和介電層結構，減少蝕刻程序中二氧化矽絕緣層及介電層結構的腐蝕損害，非常適合應用在半導體先進的奈米製程進行微小線寬的矽圖案蝕刻。 According to the second embodiment of the present invention, the present invention provides a method for etching a silicon pattern, which uses the silicon etchant described in the first embodiment of the present invention. The silicon etchant has a high silicon/silicon dioxide (Si/SiO2) etching selectivity, so it can effectively protect the structure of the silicon dioxide insulating layer and the dielectric layer, reducing the silicon dioxide insulating layer and the dielectric layer in the etching process The corrosion damage of the structure is very suitable for the etching of silicon patterns with tiny line widths in the advanced nano process of semiconductors.
以下範例係依據上述實施例所述之內容所進行的實驗，並據此做為本發明的詳細說明。 The following examples are based on the experiments described in the above embodiments and are used as a detailed description of the present invention.
範例一：矽蝕刻劑的蝕刻率測試和矽/二氧化矽(Si/SiO2)蝕刻的選擇比的評估方法 Example 1: Etching rate test of silicon etchant and evaluation method of silicon/silicon dioxide (Si/SiO2) etching selection ratio
所述的矽蝕刻劑的蝕刻率測試是在溫度為攝氏60℃的環境進行實驗。測試樣本分別是以表面是無晶型矽(a-Si)薄膜，其厚度是2000Å的晶圓(wafer)和表面是二氧化矽(SiO2)薄膜，其厚度是50Å的晶圓(wafer)作為測量矽(Si)蝕刻率和二氧化矽(SiO2)蝕刻率的測試樣本。測量蝕刻率的實驗步驟如下所述：首先以橢圓偏光測厚儀分別測量上述晶圓樣本表面薄膜的初始膜厚X Å，再將該晶圓樣本完全浸泡置入攝氏60℃的蝕刻劑中進行T(2~60)分鐘的晶圓表面薄膜蝕刻，時間到後立即取出晶圓用純水充分清洗乾淨，再以橢圓偏光測厚儀測量得到蝕刻後晶圓表面的薄膜膜厚Y Å。 The etch rate test of the silicon etchant is conducted in an environment with a temperature of 60°C. The test samples were wafers with amorphous silicon (a-Si) film on the surface and a thickness of 2000Å and wafers with silicon dioxide (SiO 2 ) on the surface and a thickness of 50Å (wafer) As a test sample for measuring the etching rate of silicon (Si) and the etching rate of silicon dioxide (SiO 2 ). The experimental steps for measuring the etch rate are as follows: First, the initial film thickness X Å of the film on the surface of the wafer sample is measured with an ellipsometric thickness gauge, and then the wafer sample is completely immersed in an etchant at 60 ℃ T (2~60) minutes of wafer surface film etching. After the time is up, take out the wafer and thoroughly clean it with pure water, and then measure the film thickness Y Å on the wafer surface after etching with an ellipsometer.
蝕刻率計算公式如以下公式
用以上述實驗方法和計算，可以分別得到矽蝕刻劑對矽(Si)和二氧化矽(SiO2)的蝕刻率。 Using the above experimental methods and calculations, the etching rate of silicon (Si) and silicon dioxide (SiO 2 ) by silicon etchant can be obtained.
最後再將Si的蝕刻率除以SiO2的蝕刻率，就可得到所述的矽蝕刻劑的矽/二氧化矽(Si/SiO2)蝕刻的選擇比。 Finally, the etching rate of Si is divided by the etching rate of SiO 2 to obtain the silicon/silicon dioxide (Si/SiO 2 ) etching selectivity of the silicon etchant.
根據範例一所述的實驗方法，分別進行實施例1~6和比較例1~5所述的矽蝕刻劑的矽/二氧化矽(Si/SiO2)蝕刻的選擇比的評估。實施例1~6和比較例1~5所使用的矽蝕刻劑組成、矽(Si)蝕刻率、二氧化矽(SiO2)蝕刻率和矽/二氧化矽(Si/SiO2)蝕刻的選擇比如表一所示。 According to the experimental method described in Example 1, the silicon/silica (Si/SiO2) etching selectivity ratios of the silicon etchant described in Examples 1 to 6 and Comparative Examples 1 to 5 were evaluated respectively. Examples of choices of silicon etchant composition, silicon (Si) etch rate, silicon dioxide (SiO 2 ) etch rate, and silicon/silicon dioxide (Si/SiO2) etch for Examples 1 to 6 and Comparative Examples 1 to 5 Table 1 shows.
根據表一所示，實施例1~6是本發明所述包含縮酮 類化合物和四級銨氫氧化物的矽蝕刻劑的實驗結果，其矽/二氧化矽(Si/SiO2)蝕刻的選擇比大於500；特別是當矽蝕刻劑的丙酮縮甘油的重量百分比是在60%以上時，其矽/二氧化矽(Si/SiO2)蝕刻的選擇比大於1000。相較之下，比較例1~4是習知不包含縮酮類化合物的矽蝕刻劑的實驗結果，其矽/二氧化矽(Si/SiO2)蝕刻的選擇比都小於500；比較例5是使用丙酮縮甘油重量百分比低於20%的矽蝕刻劑進行對照實驗，其矽/二氧化矽(Si/SiO2)蝕刻的選擇比也小於500；據此，本發明所提供的包含20~99重量%的縮酮類化合物和0.1~10重量%的四級銨氫氧化物的矽蝕刻劑相較於習知的矽蝕刻劑具有提高矽/二氧化矽(Si/SiO2)選擇比的功效。其次，因為本發明所述的矽蝕刻劑具有高於500的矽/二氧化矽(Si/SiO2)蝕刻的選擇比，所以非常適合應用在半導體先進的奈米製程進行微小線寬的矽圖案蝕刻。 According to Table 1, Examples 1 to 6 are the experimental results of the silicon etchant containing ketal compounds and quaternary ammonium hydroxide according to the present invention, and the choice of silicon/silicon dioxide (Si/SiO2) etching The ratio is greater than 500; especially when the weight percentage of acetone glycerol of the silicon etchant is more than 60%, the selectivity ratio of silicon/silicon dioxide (Si/SiO2) etching is greater than 1000. In comparison, Comparative Examples 1 to 4 are the experimental results of conventional silicon etchants that do not contain ketal compounds, and their silicon/silica (Si/SiO2) etching selectivity ratios are all less than 500; Comparative Example 5 is A silicon etch agent with a weight percentage of acetone glycerol of less than 20% was used for a control experiment, and its silicon/silica (Si/SiO2) etching selectivity ratio was also less than 500; according to this, the present invention provided 20 to 99 weight The silicon etchants of% ketal compounds and 0.1-10% by weight of quaternary ammonium hydroxide have the effect of improving the selection ratio of silicon/silica (Si/SiO 2 ) compared to the conventional silicon etchants. Secondly, because the silicon etchant of the present invention has a silicon/silicon dioxide (Si/SiO2) etching selectivity ratio higher than 500, it is very suitable for the application of advanced nano-scale semiconductor processes for etching silicon patterns with minute line widths .
以上雖以特定範例說明本發明，但並不因此限定本發明之範圍，只要不脫離本發明之要旨，熟悉本技藝者瞭解在不脫離本發明的意圖及範圍下可進行各種變形或變更。此外，摘要部分和標題僅是用來輔助專利文件搜尋之用，並非用來限制本發明之權利範圍。 Although the present invention has been described by way of specific examples, it does not limit the scope of the present invention. As long as it does not depart from the gist of the present invention, those skilled in the art will understand that various modifications or changes can be made without departing from the intention and scope of the present invention. In addition, the abstract part and title are only used to assist the search of patent documents, not to limit the scope of the present invention.
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